Low electrical resistance microporous battery separator membranes, separators, cells, batteries, and related methods

ABSTRACT

Novel or improved microporous battery separator membranes, separators, cells, batteries including such membranes, separators, or cells, and/or methods of making such membranes and/or separators, and/or methods of using such membranes and/or separators. In accordance with at least certain embodiments, an improved or novel battery separator for a secondary or rechargeable lithium battery may have low Electrical resistance of less than 0.95 ohm-cm2, or in some cases, less than 0.8 ohm-cm2. Furthermore, the inventive battery separator membrane may provide a means to achieve an improved level of battery performance in a rechargeable or secondary lithium battery based on a possibly synergistic combination of low Electrical resistance, low Gurley, low tortuosity, and/or a unique trapezoid shaped pore. In accordance with at least certain multilayer embodiments (by way of example only, a trilayer membrane made of two polypropylene layers with a polyethylene layer in between), the inventive microporous membrane or battery separator may have excellent onset and rate of thermal shutdown performance.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of Ser. No. 16/934,725filed Jul. 21, 2020, which claims priority to U.S. Divisionalapplication Ser. No. 16,378,841, filed Apr. 9, 2019, and Issued as U.S.Pat. No. 10,720,623 on Jul. 21, 2020, which claims benefit to U.S.Divisional application Ser. No. 15/172,215, filed Jun. 3, 2016 andIssued as U.S. Pat. No. 10,256, 447 on Apr. 9, 2019; which claimspriority to and the benefit of U.S. provisional patent application Ser.No. 62/170,302 filed Jun. 3, 2015, incorporated herein by reference.

FIELD OF THE INVENTION

In accordance with at least selected embodiments, the presentapplication is directed to novel or improved microporous batteryseparator membranes, separators, cells, or batteries including suchmembranes or separators, and/or methods including methods of making suchmembranes, separators, cells, and/or batteries, and/or methods of usingsuch membranes, separators, cells, and/or batteries. In accordance withat least certain embodiments, the present invention is directed to abattery separator for a secondary or rechargeable lithium battery whichmay have low electrical resistance of less than 0.95 ohm-cm², in somecases, less than 0.8 ohm-cm². In accordance with at least certainembodiments, the battery separator membrane or separator may provide ameans to achieve an improved level of battery performance in arechargeable or secondary lithium battery based on a possiblysynergistic combination of low electrical resistance, low Gurley, lowtortuosity, and/or a unique shaped pore, which pore, in some cases,approximates the shape of a trapezoid or is trapezoid-like in shape. Inaccordance with at least certain multilayer embodiments (by way ofexample only, a trilayer membranemade of two polypropylene layers with apolyethylene layer in between), the microporous membrane or batteryseparator described herein may have excellent onset of thermal shutdownand/or excellent rate of thermal shutdown performance.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 5,691,077 and 5,952,120 and U.S. Patent Publication No.2007/0148538 disclose various methods for making dry process microporousbattery separator membranes using uniaxial or machine direction (MD)stretching. The dry process (often referred to as the Celgard® process)may, in some instances, produce an elongated slit-shaped pore when usinga uniaxial mode of stretching a nonporous, semi-crystalline, extrudedpolymer precursor. Battery separator membranes made using dry processuniaxial stretch methods may, in some instances, have a machinedirection tensile strength higher than transverse directional tensilestrength.

In order to increase the transverse directional tensile strength forvarious dry process porous separator membranes, U.S. Pat. No. 8,795,565and U.S. Patent Publication Nos. 2011/0223486, 2014/0287322 and2014/0302374 propose various methods including transverse direction (TD)stretching, performed simultaneously and/or sequentially with machinedirection (MD) stretching (or uniaxial stretching).

U.S. Pat. No. 8,795,565 and U.S. Patent Publication Nos. 2014/0287322and 2014/0302374 propose various transverse direction stretching methodswhich may include a simultaneous controlled machine direction relaxstep, a MD/TD stretch ratio of about 0.5 to about 4.0, and/or a MDtensile strength of up to about 1450 kg/cm². The unique stretchingprocesses may, in some instances, result in a change in the shape of thepores from an elongated slit-shape pore that may be found with some dryprocess uniaxial stretching processes, to a more round-shape pore (or asubstantially round-shaped pore). Pore size and shape may be, in someinstances, important separator membrane performance properties becausethey may influence the migration of electrolyte and ions between theelectrodes of a lithium ion rechargeable battery during the charge anddischarge cycles. U.S. Patent Publication No. 2011/0223486 proposes, invarious embodiments, an adjustment in the amount of MD and TD stretchingwhere the MD/TD stretch ratio is approximately equal to one, in order toproduce a porous membrane with balanced MD and TD tensile strength. Andin various instances, ER values of known biaxial stretched dry processbattery separator membranes may be greater than 1 ohm-cm².

SUMMARY OF THE INVENTION

The details of one or more embodiments are set forth in the descriptionsbelow. Other features, objects, and advantages will be apparent from thedescription and from the claims.

The power performance of various lithium batteries, such as secondary orrechargeable lithium ion batteries, may be limited or influenced by theER, the Gurley and/or the tortuosity of the battery separator used insuch a battery. There is a need for a microporous separator membranewith very low ER, low Gurley and low tortuosity in order to increase thepower, improve the rate performance, improve the cycling performance,improve the cycle life, and/or improve performance after a high numberof charge/discharge cycles of a lithium ion rechargeable battery. Insome instances, an improved separator having a very low ER, low Gurley,and low tortuosity may provide a separator having lower ionic resistanceto the flow of electrolyte during battery cycling, which may contributeto various improvements in performance for a battery containing such animproved separator. Electric Drive Vehicles (EDVs) often require a highpower performance battery. One method of achieving higher powerperformance in a lithium ion battery for EDV end use applications is touse a very low ER, microporous separator membrane with low Gurley andlow tortuosity in a lithium ion rechargeable battery.

In accordance with at least selected embodiments, the presentapplication or invention is directed to an improved or novel microporousbattery separator membrane for a lithium rechargeable battery, such as alithium ion battery, and various methods of making such separatormembranes. The battery separator described herein can have a lowelectrical resistance (ER) of, in some instances, less than 0.95ohm-cm², and in some cases, less than 0.8 ohm-cm², low Gurley, lowtortuosity and a unique non-round shaped pore. The method of achievinglow ER, low Gurley, low tortuosity and a non-round shaped pore (such asa pore whose shape approximates a trapezoid or is trapezoid-like) may bebased on novel methods to control the pore size during machine directionand/or transverse directional stretching processes.

In accordance with at least selected embodiments, the presentapplication or invention may address the above needs or demands and/oris directed to novel or improved separator membranes, separators,batteries including such separators, methods of making such membranes,separators and/or batteries, and/or methods of using such membranes,separators, and/or batteries. The instant invention relates to a new orimproved microporous separator membrane for a lithium ion battery andmethods of manufacture and use thereof. The possibly preferred inventivemicroporous separator membrane is stretched in a novel method whichvaries the mode of the uniaxial (machine) and transverse directionstretching process steps.

In addition, the nonporous precursor membrane is a highly crystalline.The highly crystalline nonporous precursor is initially machinedirection stretched where the amount of MD stretching is conducted toproduce a high percent transverse direction elongation (% TD elongation)“semi-porous intermediate” membrane. The initial MD stretching of ahighly crystalline nonporous precursor produces a semi-porousintermediate with % TD Elongation that is, in some embodiments, greaterthan 600% and/or a puncture strength that is, in some embodiments,greater than 330 gf, in some embodiments, greater than 350 gf, whichproperties may be important in achieving the inventive low ERmicroporous separator membrane described in various embodiments herein.Table 1 lists various properties of the semi-porous intermediatemembrane. The semi-porous intermediate is not a finished product, but isan intermediate membrane which has, in certain embodiments, a targetedpuncture strength, and/or a targeted % TD elongation. In variousembodiments, the semi-porous intermediate is next transverse directionalstretched at a preferred temperature and speed where the TD stretchingprocess is followed by a TD relax step performed preferably at 120 to140° C. Table 4 lists the separator properties of the final MD and TDstretched microporous battery separator membranes made according tovarious embodiments described herein.

In accordance with selected embodiments, the microporous separatormembrane has low electrical resistance (ER) of less than 0.95 ohm-cm²,and in some cases, less than 0.8 ohm-cm² combined with low Gurley andlow tortuosity. In addition, the microporous separator membrane has aunique morphology as evidenced in scanning electron micrographs (SEMs)shown in FIGS. 9 through 13 . The unique porous structure differs fromthat of known dry process uniaxial and biaxial stretched porousseparator membranes (such as the membranes whose SEMs are included inFIGS. 3 through 8 ). The porous structure of the membrane described invarious embodiments herein may resemble a “knitted-like” structurewherein the polymer crystalline lamellae regions resemble small islandsconnected by a 3-D array of vertically and diagonally elongatedfibrillar structures. In addition, in some embodiments, the pores mayappear to have a four-sided trapezoid-like shape or a shape that in someways approximates the shape of a trapezoid. The unique pore shape of theporous structure of these membranes appears to be different from thesubstantially round-shaped pores of certain known biaxially stretcheddry process microporous battery separator membranes, and different fromthe elongated slit-shaped pores of certain known uniaxially stretcheddry process microporous battery separator membranes. Such differences inpore shape are shown, with approximations only, in FIG. 1 . The shape ofthe pores may, in some instances, play an important role in theperformance of the microporous battery separator membrane, together withthe ER, Gurley, tortuosity and overall porosity of such a microporousbattery separator membrane, since the pores provide electrolyte storageand also form a tortuous pathway for the transport of ions between anodeand cathode via an electrolyte medium during the charge and dischargecycles in a lithium ion rechargeable battery.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts several approximations of the pore shapes of variousmicroporous separator membranes according to embodiments describedherein, compared with approximated pore shapes for comparative CE1 andCE3 microporous separator membranes.

FIG. 2 includes a plot of electrical resistance (ER) as a function oftemperature for various trilayer microporous battery separator membranesformed as part of Examples 1-4.

FIG. 3 includes a Scanning Electron Micrograph (SEM) image, at 20,000×magnification, of the surface of a commercially available microporousmonolayer polypropylene separator membrane known as Celgard® 2500, whichis about 25 microns thick.

FIG. 4 includes an SEM image, at 5,000× magnification, of the surface ofa commercially available Celgard® 2500 separator membrane.

FIG. 5 includes an SEM image, at 20,000× magnification, of the crosssection of a commercially available Celgard® 2500 separator membrane.

FIG. 6 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous monolayer polypropylene separator membrane made inaccordance with CE1 (Comparative Example 1) herein.

FIG. 7 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous trilayer PP/PE/PP separator membrane made inaccordance with CE2 (Comparative Example 2) herein.

FIG. 8 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous monolayer polypropylene separator membrane made inaccordance with CE5 (Comparative Example 5) herein.

FIG. 9 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous PP/PE/PP separator membrane made in accordance withExample 2.

FIG. 10 includes an SEM image, at 5,000× magnification, of the surfaceof the microporous PP/PE/PP separator membrane made in accordance withExample 2.

FIG. 11 includes an SEM image, at 4,800× magnification, of the crosssection of the microporous PP/PE/PP separator membrane made inaccordance with Example 2.

FIG. 12 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous monolayer PP separator membrane made in accordancewith Example 6.

FIG. 13 includes an SEM image, at 20,000× magnification, of the surfaceof the microporous monolayer PP separator membrane made in accordancewith Example 7.

DETAILED DESCRIPTION OF THE INVENTION

Before the present membranes, separators, cells, batteries, methods,and/or the like are disclosed and described, it is to be understood thatthey are not limited to specific methods, components, particularcompositions, or the like. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Ranges may be expressed herein as from “about” oneparticular value, and/or to “about” another particular value. When sucha range is expressed, another embodiment includes from the oneparticular value and/or to the other particular value. Similarly, whenvalues are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value forms anotherembodiment. It will be further understood that the endpoints of each ofthe ranges are significant both in relation to the other endpoint, andindependently of the other endpoint.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not. Throughout the description and claims of this specification,the word “comprise” and variations of the word, such as “comprising” and“comprises,” means “including but not limited to,” and is not intendedto exclude, for example, other additives, components, integers or steps.“Exemplary” means “an example of” and is not intended to convey anindication of a preferred or ideal embodiment. “Such as” is not used ina restrictive sense, but for explanatory purposes.

Disclosed are products, shapes, pores, components, materials, layers, orthe like that can be used to perform the disclosed characteristics,performance, methods, and systems. These and other components aredisclosed herein, and it is understood that when combinations, subsets,interactions, groups, etc. of these components are disclosed that whilespecific reference of each various individual and collectivecombinations and permutation of these may not be explicitly disclosed,each is specifically contemplated and described herein, for allproducts, methods and systems. This applies to all aspects of thisapplication including, but not limited to, steps in disclosed methods.Thus, if there are a variety of additional steps that can be performedit is understood that each of these additional steps can be performedwith any specific embodiment or combination of embodiments of thedisclosed methods.

In accordance with selected embodiments, the present invention isdirected to a microporous membrane which comprises a thermoplasticpolymer which can be characterized as semi-crystalline polymer. Suchpolymers may include polypropylene (PP), polyethylenes (LDPE, LLDPE,HDPE, and UHMWPE), polybutene, polymethylpentene, co-polymers thereof,and blends or mixtures thereof. The polyolefin can be a homopolymer or ablend of homopolymer polyolefins. The polyolefin can be a co-polymer ora blend of co-polymers of polyolefins. In one embodiment, the preferredpolyolefin can be a polypropylene which has a melt flow index (mfi) lessthan 1.0 g/10 minutes. In another embodiment, the preferred polyolefincan be a polyethylene which has an mfi less than 0.5 g/10 minutes.

The microporous membrane of the present invention may be a single-ply ormulti-ply microporous membrane. In general, in accordance with selectedembodiments, the process for making the inventive microporous membranemay include the steps of extruding a blown film nonporous precursor inthe form of a bubble using an annular die and flattening this tubularbubble membrane to form a “collapsed bubble” nonporous membrane asdescribed in U.S. Pat. No. 5,952,120 and in U.S. Patent Publication No.2007/0148538, In accordance with at least selected embodiments, thenonporous precursor may be a collapsed bubble polypropylene (PP)membrane. In accordance other embodiments, the nonporous precursor is amulti-ply precursor membrane comprising two outer plies of polypropylene(PP) precursor sandwiching a center ply of polyethylene (PE) precursorwhich form a stacked precursor membrane with a PP/PE/PP configuration.In some embodiments, such a multi-ply precursor membrane is formed vialamination of the PP/PE/PP precursor membranes together. In otherembodiments, the nonporous precursor is a multi-ply precursor membranethat is produced by co-extruding polypropylene (PP)/polyethylene(PE)/polypropylene (PP) to form a nonporous trilayer precursor membranewith a PP/PE/PP configuration and collapsing the PP/PE/PP trilayerprecursor bubble to form a multi-ply PP/PE/PP precursor membrane.

A nonporous monolayer or multilayer precursor membrane can be annealedto increase the amount and size of the crystalline lamallae in theprecursor membrane in order to increase the percent crystallinity of theprecursor membrane.

In one embodiment of the separator membrane described herein, thenonporous coextruded PP/PE/PP or laminated stacked PP/PE/PP precursormembrane is initially stretched in the machine direction (MD). Theamount of MD stretching can be selected or optimized to produce asemi-porous intermediate membrane with high transverse direction (TD)percent elongation, preferably greater than about 600%. Such asemi-porous intermediate membrane having a high percent TD elongationmay play a role in achieving the desired amount of ID stretching in asubsequent transverse stretching process step. Furthermore, the amountof MD stretch performed on the nonporous precursor can be optimized toproduce a certain percent porosity in semi-porous intermediate membrane,preferably 20 to 50% porosity, in some embodiments, about 30 to 50%porosity. In addition, the amount of MD stretch performed on thenonporous precursor membrane can be optimized to produce a semi-porousintermediate membrane with excellent puncture strength greater than 330gf.

Following the MD stretching process step, the semi-porous intermediatemembrane can be transverse stretched, preferably using 15-400% stretchratio, in some embodiments, 20-250% stretch ratio, more preferably25-100% stretch ratio, where the stretch ratio is defined as the“difference of the (final width of the membrane the initial width of themembrane) divided by the initial width of the membrane”. TD stretchingcan be performed preferably at a temperature of 100-130° C. where theline speed is 25-250 ft./minute, in some cases, 50-200 ft./minute, andin some cases, 50-100 ft./minute.

Following the TD stretching process step, the microporous trilayerseparator membrane can be transverse direction (TD) relaxed preferablyat 10-50% and more preferably at 20-40%. TD relax can be performed at atemperature of preferably 120-140° C.

Following the TD relax process step, the microporous trilayer separatormembrane can be heat treated to stabilize the membrane preferably at atemperature of 60° C. to 100° C. for preferably 8 hours to 2 to 3 days.

The microporous PP/PE/PP battery separator membrane has a thermalshutdown function due to the inner PE layer. Thermal shutdown isdetermined by measuring the impedance while the temperature is linearlyincreased. Thermal shutdown is defined as the temperature at which theimpedance or the electrical resistance (ER) increases thousand-fold. Athousand-fold increase in impedance may be needed for a batteryseparator membrane to stop thermal runaway in a lithium ion battery. Therise in impedance corresponds to a collapse in the pore structure due tothe melting of the separator. During thermal shutdown, the pores of theinner PE layer of the possibly preferred inventive separator membranecan coalesce and close at a temperature of 130-135° C. causing thethousand-fold increase in impedance shown in FIG. 2 .

Thermal shutdown can be affected by several separator parameters such asER, Gurley, pore size, tortuosity, and/or porosity. A balance of theseparameters can play an important role in achieving a low onsettemperature of thermal shutdown.

The excellent onset temperature of thermal shutdown of the possiblypreferred inventive microporous membranes is achieved, in someembodiments, by controlling the increase in pore size which occursduring transverse stretching. Transverse stretching of the semi-porousintermediate membrane can be used to produce a pore size in the range of0.03-0.08 μm, in some cases, 0.04-0.06 μm in the polypropylene layers inthe trilayer membrane, which is larger than the typical pore size ofuniaxial dry stretched polypropylene layers in a known multilayerPP/PE/PP microporous membrane. By controlling the pore size reachedduring the transverse stretching step, the process for the possiblypreferred inventive membrane produces a microporous multilayer separatormembrane with a combination of a low ER less than 0.95 ohm-cm2, in somecases, even less (e.g., less than 0.9, less than 0.8, less than 0.7,less than 0.6, and so forth), a low Gurley less than 150 seconds/100 ccand a low tortuosity of less than 1.2.

In another embodiment of making a separator membrane according tovarious embodiments herein, the nonporous monolayer polypropyleneprecursor membrane is initially machine direction (MD) stretched toproduce a “semi-porous intermediate” membrane. The amount of MDstretching is preferably selected to produce a “semi-porousintermediate” membrane with high transverse direction (TD) percentelongation, preferably greater than 600%. Furthermore, the amount of MDstretch is optimized to produce a “semi-porous intermediate” membranewith a certain porosity, preferably 20-50%, and in some cases, 30-50%.In addition, the amount of MD stretch is optimized to produce a“semi-porous intermediate” membrane, here a monolayer membrane, withgood puncture strength greater than 350 gf.

Following the MD stretch step, the monolayer porous membrane istransverse stretched preferably using 15-400% stretch ratio, in somecases, 20-250% stretch ration, and in still some cases, 25-100% stretchratio where the stretch ratio is defined as the “(final width of themembrane—the initial width of the membrane) divided by the initial widthof the membrane”. TD stretching is performed preferably at a temperatureof 100-130° C. at a speed of preferably 25-250 ft./minute, in somecases, 50-200 ft./minute, and in some cases, 50-100 ft./minute.

Following TD stretching, the microporous monolayer separator membranecan be Transverse direction (TD) relaxed preferably at 10-50% TD relaxand more preferably at 20-40% TD relax. TD relax temperature ispreferably 120-140° C.

Following TD relax, the microporous monolayer separator membrane can beheat treated to stabilize the membrane, preferably at a temperature of60° C. to 100° C. for preferably 8 hours to 2 to 3 days.

Furthermore, the inventive monolayer microporous separator membrane hasin certain embodiments, an ER of less than 0.95 ohm-cm² (and in somecases, less than 0.9, or less than 0.85, or less than 0.8, and so forth)and a puncture strength>250 gf. The inventive microporous monolayerbattery separator membrane preferably has a combination of low ER, lowGurley and low tortuosity, and at the same time, the pore size has beencontrolled to be in the range of 0.03-0.08 μm, in some cases, 0.04-0.06μm, and in some cases 0.050 to 0.060 μm, and the porosity of theinventive monolayer separator membrane to be preferably in the range of60-70% using TD stretching.

The possibly preferred inventive multilayer and monolayer microporousbattery separator membranes have low tortuosity less than 1.3.Tortuosity may be described as a measure of the winding path the ionstravel from one surface of the face of a porous membrane, through thepores in the body of the membrane, to the opposite outer face of themembrane. Low tortuosity facilitates more movement or quicker movementof ions and electrolyte through a porous battery separator membrane(compared with high tortuosity) during the charge and discharge cyclesof a lithium ion battery. In some instances, a low tortuosity membranecan contribute to a lithium ion battery having a higher rate of cyclingand an improved cycle life performance. During the charge cycle of alithium rechargeable battery, which may have carbon based or lithiummetal anodes, lithium ions are transported from the cathode via theelectrolyte medium through the pores of the separator membrane to theanode of the battery. The opposite occurs during discharge cycle wherelithium ions move from the anode to the cathode. With continuous chargeand discharge cycling, a low tortuosity membrane may, in some instances,increase the rate of cycling, electrode utilization and electrodecycling which may, in some instances, improve the cycle life performanceof a lithium rechargeable battery.

EXAMPLES

In the following Tables 1 to 4, separator membrane property data islisted for examples produced using the foregoing described process.Table 1 lists two key properties of a semi-porous trilayer (PP/PE/PP)intermediate produced after an initial MD stretch process step in whichMD stretching is conducted to produce a semi-porous trilayer (PP/PE/PP)intermediate membrane where the percent TD elongation is greater than600% and a puncture strength of the semi-porous intermediate membrane isgreater than 330 gf.

TABLE 1 Property Value % TD Elongation of semi-porous trilayer >600(PP/PE/PP) intermediate Puncture strength of semi-porous trilayer >330(PP/PE/PP) intermediate, gf

TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 CE 2 CE 3 CE 4 Thickness, μm 16 16 17 1617.2 16 16 Gurley (JIS), 30 60 100 150 500 460 460 sec/100 cc Porosity,% 63 56 50 48 49 35 39 ER, ohm-cm² 0.30 0.45 0.57 0.47 0.50 1.9 2.1Tortuosity 1.0 1.2 1.2 1.1 na 1.9 >1.9 PP pore size, μm 0.051 0.0490.048 0.046 0.065 0.032 0.026 Pore Shape

trapezoid-like or Round Elongated Elongated approximating a shape like aor rectangular rectangular trapezoid substan- slit slit tially roundShutdown Onset 127.5 130 129 131 130 129 130 Temperature, ° C. MDtensile 1200 1500 1743 1900 646 1700 2100 strength, kg/cm² TD tensile200 170- 160 150 730 160 150 strength, 180 kg/cm² % MD elongation 41 4547 42 na na 40-50 % TD elongation 335 533 711 760 na 100 300 PunctureStrength, 250 280 320 350 364 >250 280 gf Mixed Penetration −60% −42%−40% −35% na −30% −25%

Table 2 lists separator property and performance data on InventiveExample 1, Example 2, Example 3 and Example 4 (all four trilayerseparator membranes made according to the processes described herein)together with Comparative example CE 2, Comparative example CE 3 andComparative example CE 4. CE 2 is a biaxial MD/TD stretched dry processmicroporous trilayer microporous membrane. Comparative example CE 3 is auniaxial MD stretched dry process laminated trilayer microporousmembrane, and Comparative example CE 4 is a uniaxial MD stretched dryprocess co-extruded trilayer microporous membrane.

In accordance with selected embodiments shown in these Examples, theinventive trilayer microporous separator membrane has very lowelectrical resistance (ER) of 0.57 ohm-cm² or less, a low Gurley of 150sec/100 cc or less, and a low tortuosity of 1.2 or less. CE 2 is abiaxial stretched trilayer microporous membrane with low ER but it has ahigh Gurley and much lower MD tensile strength both of which areseparator properties which can affect battery cycle performance. Theinventive separator membrane has significantly improved lower ER, lowertortuosity and lower Gurley than CE 3 and CE 4 which are porousmembranes made without any transverse direction stretching. Theuniqueness of the inventive separator membrane is demonstrated by itsnovel morphology as evidenced by Scanning Electron Micrograph (SEM)analysis. FIG. 9 shows an SEM image of the inventive Ex. 2 which hasunique pore shape that is different from the pore shape of known dryprocess biaxial stretched porous separator membranes (such as themembrane shown in FIG. 7 ). The porous structure of the inventivemembrane resembles a “knitted-like” structure where the polymercrystalline lamellae regions resemble small islands connected by a 3-Darray of vertically and diagonally elongated fibrillar structures. Thepores of the separator membrane of Ex. 2, shown in FIGS. 9 and 10 , havea non-rounded shape and may be described as having approximately a foursided geometric shape which is similar to an isosceles trapezoid or apore shape that is trapezoid-like in appearance. This novel shaped poremay, in certain instances, provide various advantages to one or moreseparators when compared to other battery separator membranes such as 1)other known biaxial direction stretched dry process microporous batteryseparator membranes which may have a round-shaped or substantiallyround-shaped pore as shown in FIG. 7 , and/or 2) other known uniaxialdirection stretched dry process microporous battery separator membranesshown in FIGS. 3, 4 and 5 .

The excellent onset of thermal shutdown of the possibly preferredinventive trilayer microporous membrane may be achieved by controllingthe increase in pore size which occurs during transverse stretching.Transverse stretching of the semi-porous intermediate inventive membraneproduced polypropylene layers in the trilayer membrane with a pore sizeof 0.046 to 0.051 μm, which is shown to be larger than the typical poresize of various uniaxial stretched polypropylene layers in multilayer CE3 and CE 4 microporous membranes. In addition to smaller PP pore sizes,the possibly preferred inventive microporous separator membrane has acombination of a very low ER, in some cases, less than 0.57 ohm-cm², alow Gurley, in some cases, less than 150 seconds/100cc in combinationwith a low tortuosity, in some cases of less than 1.2.

Table 3 lists two properties of the semi-porous monolayer intermediateproduced in the initial MD stretch process step in which MD stretchingis conducted to produce a semi-porous intermediate membrane where thepercent TD elongation is greater than 600% and a puncture strength ofthe semi-porous intermediate membrane is greater than 350 gf.

TABLE 3 Property Value % TD Elongation of monolayer >600 semi-porousintermediate Puncture strength of monolayer >350 semi-porousintermediate, gf

Table 4 lists separator property and performance data on InventiveExample 5, Example 6 and Example 7, all of which are monolayerpolypropylene separator membranes made in accordance with the processesdescribed herein, together with Comparative example CE 1, Comparativeexample CE 5 and Comparative example CE 6. Comparative example CE 1 is amonolayer biaxial stretched microporous separator membrane, Comparativeexample CE 5 is a beta nucleated monolayer biaxial stretched microporousseparator membrane, and Comparative example CE 6 is a monolayer uniaxialMD stretched microporous separator membrane.

TABLE 4 Ex. 5 Ex. 6 Ex. 7 CE 1 CE 5 CE 6 Thickness, μm 25 24 23 15 30 25Gurley (JIS), 120 90 50 500 370 200 sec/100 cc Porosity, % 60 62 68 6961 41 ER, ohm-cm² 0.77 0.70 0.63 0.50 2.0 1.5 Tortuosity 1.3 1.3 1.3 1.42.1 1.7 PP pore size, 0.050 0.055 0.060 0.065 0.060 0.043 μm ShutdownOnset 164 166 168 >150 >165 >165 Temperature, ° C. MD tensile 1200 11001000 800 850 1420 strength, kg/cm² TD tensile 130 160 180 500 648 140strength, kg/cm² Puncture 320 250 260 230 >400 >450 Strength, g

In accordance with selected embodiments, the inventive monolayermicroporous separator membrane has very low electrical resistance (ER)of 0.77 ohm-cm² or less, and low Gurley of 120 seconds/100 cc or less incombination with low tortuosity of about 1.3 or less.

Inventive Example 5, Inventive Example 6 and Inventive Example 7 have aGurley of 120 sec/100 c or less which is significantly lower than CE 1,CE 5 and CE 6. The biaxial stretched CE 5 has a larger pore size andhigher tortuosity when compared to the inventive membrane but has higherER. The uniaxial stretched CE 6 has higher tortuosity and comparativepore size but has much higher ER. CE 1 has comparative ER to theinventive membrane, however, this is at the expense of higher Gurley andmuch lower machine direction tensile strength.

The synergistic combination of low ER, low Gurley and low tortuosity inthe inventive monolayer separator membrane may be attributable to theporous structure which resembles the same “knitted-like” structure ofthe inventive trilayer membrane discussed in various embodiments abovewhere the polymer crystalline lamellae regions resemble small islandsconnected by a 3-D array of vertically and diagonally elongatedfibrillar structures as the inventive trilayer separator membrane. Theinventive monolayer membrane also has a unique morphology as evidencedin Scanning Electron Micrograph (SEM) analysis. The SEM images of thesurface of the inventive monolayer Ex. 6 and Ex. 7 are shown in FIGS. 12and 13 , respectively. The pores of the inventive monolayer microporousmembrane have the same non-round pore shape as the inventive trilayermicroporous membrane. The inventive monolayer microporous membrane has apore shape which is different from 1) various known dry process uniaxialstretched monolayer porous separator membranes (such as the one shown inFIG. 6 ) which has the elongated slit-shaped pore typical of uniaxialCelgard® dry process battery separator membranes, and 2) the prior artdry process beta-nucleated biaxial stretched porous separator membranesshown in FIG. 8 which has vein-like porous structure with a thick,intertwined lamellar fibrous structure typical of a beta-nucleatedpolypropylene porous membrane.

The excellent onset of thermal shutdown of the inventive monolayermicroporous membrane is achieved by controlling the increase in poresize which occurs during transverse stretching process step. Transversestretching of the inventive monolayer membrane which followed the MDstretching of the semi-porous intermediate membrane can produce poresize of 0.050 to 0.060 μm which are smaller than that of the biaxialstretched CE 1. Smaller pore size can contribute to effective closure ofthe pores at thermal shutdown and a faster rate of thermal shutdown.

The inventive battery separator membrane may provide a means to achievean improved level of battery performance in a rechargeable or secondarylithium battery based on a synergistic combination of low electricalresistance with low Gurley, low tortuosity and a unique non-roundtrapezoid (interior angles less than 90 degrees) shaped pore.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.Additionally, the invention illustratively disclosed herein suitably maybe practiced in the absence of any element which is not specificallydisclosed herein.

TEST METHODS Thickness

Thickness is measured using the Emveco Microgage 210-A precisionmicrometer thickness tester according to test procedure ASTM D374.Thickness values are reported in units of micrometers, μm.

Gurley

Gurley is defined as the Japanese Industrial Standard (JIS Gurley) JISP8117 and is an air permeability test measured using the OHKENpermeability tester. JIS Gurley is the time in seconds required for 100cc of air to pass through one square inch of film at constant pressureof 4.8 inches of water.

Puncture Strength

Test samples are first pre-conditioned to 73.4 deg C. and a relativehumidity of 50% for a minimum of 20 minutes. An Instron Model 4442 isused to measure puncture strength of test sample. Thirty measurementsare made across the diagonal direction of a 1¼″×40″ continuous samplespecimen and averaged. The needle has a 0.5 mm radius. The rate ofdescent is 25 mm/min. The film is held tight in a clamping device whichutilizes an O-ring to securely hold the test sample in place. Thediameter of this secured area is 25 mm. The displacement (in mm) of thefilm that was pierced by the needle is recorded against the resistanceforce (in gram force) developed by the tested film. The maximumresistance force is the puncture strength in units of gram force (gf). Aload-versus-displacement plot is produced by this test method.

Pore Size

Pore size is measured using the Aquapore Porosimeter available throughPorous Materials, Inc. (PMI). Pore size is expressed in μm.

Porosity

The porosity of a microporous film sample is measured using ASTM methodD-2873 and is defined as the percent void spaces in a microporousmembrane.

TD and MD Tensile Strength

The tensile strength along the MD and TD is measured using Instron Model4201 according to ASTM D-882 method.

Electrical Resistance (ER) (Also Known as Ionic Resistance, IR)

Electrical Resistance is defined as the Resistance value in ohm-cm2 of aseparator filled with electrolyte. The units of electrical resistanceare ohm-cm². The separator resistance is characterized by cutting smallpieces of separators from the finished material and then placing thembetween two blocking electrodes. The separators are saturated with thebattery electrolyte with 1.0 M LiPF₆ salt in EC/EMC solvent of 3:7 ratioby volume. The Resistance, R, in Ohms (Ω), of the separator is measuredby a 4-probe AC impedance technique. In order to reduce the measurementerror on the electrode/separator interface, multiple measurements areneeded by adding more layers. Based on the multiple layer measurements,the electric (ionic) resistance, R_(s) (Ω), of the separator saturatedwith electrolyte is then calculated by the formula R_(s)=p_(s)l/A wherep_(s) is the ionic resistivity of the separator in Ω-cm, A is theelectrode area in cm² and l is the thickness of the separator in cm. Theratio p_(s)/A=is the slope calculated for the variation of the separatorresistance (ΔR) with multiple layers (Δδ) which is given byslope=p_(s)/A=ΔR/Δδ.

Hot Electrical Resistance (ER)

Hot Electrical Resistance is a measure of resistance of a separator filmunder 50 lb pressure while the temperature is linearly increased at arate of 60° C./minute. A ⅜″ diameter piece of separator is saturatedwith electrolyte and sandwiched between two electrode discs made of Alor Cu. The rise in resistance, measured as Impedance, corresponds to acollapse in pore structure due to melting or “shutdown” of the separatorMembrane. When a separator membrane has sustained high level ofelectrical resistance at elevated temperatures, this is indicative thatthe separator membrane may prevent electrode shorting in a battery.

Mixed Penetration

Mixed Penetration is the force required to create a short through aseparator when placed between cathode and anode materials. This test isused to indicate the tendency of a separator to allow short circuitsduring the battery assembly. Details of this method are described in US2010/209758.

Dielectric Breakdown (DB)

Dielectric breakdown (DB) is the measurement of the electricalinsulation property of a separator. Voltage is applied to a separatormembrane at a ramp rate of 6,000V/sec until the dielectric breakdown ofthe sample is observed. High DB is indicative that the separator willhave good winding yields and low HiPot failure rate.

Tortuosity

Tortuosity, τ, is calculated using the following formula where A is themembrane area in cm², R is membrane resistance in ohm cm (Ω cm), ε isthe percent porosity, L is the thickness of the membrane and ζ is theelectrolyte resistance in Ohm cm (Ω cm):

τ² = A × R × ɛ/(L × ζ)

In accordance with at least selected embodiments, aspects or objects,the present application or invention is directed to novel or improvedmicroporous battery separator membranes, separators, cells, or batteriesincluding such membranes or separators, and/or methods including methodsof making such membranes, separators, cells, and/or batteries, and/ormethods of using such membranes, separators, cells, and/or batteries. Inaccordance with at least certain embodiments, the present invention isdirected to a battery separator for a secondary or rechargeable lithiumbattery which may have low electrical resistance of less than 0.95ohm-cm², in some cases, less than 0.8 ohm-cm². In accordance with atleast certain embodiments, the battery separator membrane or separatormay provide a means to achieve an improved level of battery performancein a rechargeable or secondary lithium battery based on a possiblysynergistic combination of low electrical resistance, low Gurley, lowtortuosity, and/or a unique shaped pore, which pore, in some cases,approximates the shape of a trapezoid or is trapezoid-like in shape. Inaccordance with at least certain multilayer embodiments (by way ofexample only, a trilayer membrane made of two polypropylene layers witha polyethylene layer in between), the microporous membrane or batteryseparator described herein may have excellent onset of thermal shutdownand/or excellent rate of thermal shutdown performance.

In accordance with at least certain embodiments, aspects or objects,there are provided novel or improved microporous battery separatormembranes, separators, cells, batteries including such membranes,separators, or cells, and/or methods of making such membranes and/orseparators, and/or methods of using such membranes and/or separators. Inaccordance with at least certain embodiments, an improved or novelbattery separator for a secondary or rechargeable lithium battery mayhave low Electrical resistance of less than 0.95 ohm-cm², in some cases,less than 0.8 ohm-cm². Furthermore, the inventive battery separatormembrane may provide a means to achieve an improved level of batteryperformance in a rechargeable or secondary lithium battery based on apossibly synergistic combination of low Electrical resistance, lowGurley, low tortuosity, and/or a unique trapezoid shaped pore. Inaccordance with at least certain multilayer embodiments (by way ofexample only, a trilayer membrane made of two polypropylene layers witha polyethylene layer in between), the inventive microporous membrane orbattery separator may have excellent onset and rate of thermal shutdownperformance which may be achieved by controlling an increase in poresize using transverse stretching.

In accordance with at least certain embodiments, aspects or objects, thepresent disclosure or invention may address the above needs, issues,problems, or desires for better or enhanced power performance of variouslithium batteries, such as secondary or rechargeable lithium ionbatteries, may be influenced by the ER, the Gurley and/or the tortuosityof the battery separator used in such a battery. There is a need for amicroporous separator membrane with very low ER, low Gurley and lowtortuosity in order to increase the power, improve the rate performance,improve the cycling performance, improve the cycle life, and/or improveperformance after a high number of charge/discharge cycles of a lithiumion rechargeable battery. In some instances, an improved separatorhaving a very low ER, low Gurley, and low tortuosity may provide aseparator having lower ionic resistance to the flow of electrolyteduring battery cycling, which may contribute to various improvements inperformance for a battery containing such an improved separator.Electric Drive Vehicles (EDVs) often require a high power performancebattery. One method of achieving higher power performance in a lithiumion battery for EDV end use applications is to use a very low ER,microporous separator membrane with low Gurley and low tortuosity in alithium ion rechargeable battery.

In accordance with certain embodiments, there are provided novel orimproved microporous battery separator membranes, separators, cells,batteries, and/or a novel, improved or modified polyolefin batteryseparator membrane, comprising:

a microporous separator membrane having an electrical resistance lessthan 0.95 ohm-cm² or less than 0.8 ohm-cm²,

a microporous separator membrane having a Gurley less than 150 sec/100cc,

a microporous separator membrane having a tortuosity less than 1.3,

wherein said microporous polyolefin separator membrane has a non-round,trapezoid shape pore, and/or where said improved and modifiedmicroporous polyolefin separator membrane consists of a polypropylene,polyethylene, mixtures thereof, and co-polymers thereof, where saidimproved and modified microporous polyolefin separator membrane can be amonolayer membrane, where said improved and modified microporouspolyolefin separator membrane can be a multilayer membrane with athermal shutdown function, where said improved and modified microporouspolyolefin separator membrane can be a multilayer membrane consisting ofa trilayer of polypropylene/polyethylene/polyethylene, wherein the saidimproved and modified microporous polyolefin separator membrane has athickness less than 25 μm, and/or wherein the said improved and modifiedmicroporous polyolefin separator membrane has pores with a non-round,trapezoid shape, and/or a novel, improved or modified polyolefin batteryseparator membrane made by a process comprising:

extruding a polypropylene which has a melt flow index less than 1.0 g/10minutes to form a monolayer nonporous precursor membrane and,

machine direction stretching a nonporous polypropylene precursormembrane to form a semi-porous intermediate membrane having a puncturestrength>350 gf and TD elongation>600%, transverse direction stretchinga semi-porous intermediate membrane using a stretch ratio of 15 to 400%,and preferably stretching using a stretch ratio of 25 to 100% to form amicroporous separator membrane, and/or formed when said semi-porousintermediate membrane is transverse stretched at a temperature of 100 to130 deg C., formed wherein said semi-porous intermediate membrane istransverse stretched at a temperature of 100 to 130 deg C. at a speed of100 ft/minute, and preferably at a speed of 50 ft/minute, whereinmembrane is thermally relaxed at 120 to 140 deg C., and/or whereinmembrane is heat treated at a temperature of 60 to 100 deg C. forpreferably 8 hours to 2 to 3 days, and/or a novel, improved or modifiedpolyolefin trilayer battery separator membrane made by a processcomprising:

extruding a polyethylene which has a melt flow index less than 1.0 g/10minutes to form a monolayer nonporous polyethylene precursor membraneand,

extruding a polypropylene which has a melt flow index less than 1.0 g/10minutes to form a monolayer nonporous polypropylene precursor membraneand,

laminating two plies of polypropylene precursor membrane as outer plies(layers) sandwiching one inner ply (layer) of polyethylene precursormembrane to form a trilayer polypropylene/polyethylene/polyethylenenonporous precursor,

machine direction stretching a nonporouspolypropylene/polyethylene/polyethylene precursor membrane to form asemi-porous intermediate membrane having a puncture strength>350 gf andTD elongation>600%,

transverse direction stretching a semi-porous intermediate membraneusing a stretch ratio of 15 to 400%, and preferably stretching using astretch ratio of 25 to 100% to form a microporous trilayer separatormembrane, and/or formed when said semi-porous intermediate membrane istransverse stretched at a temperature of 100 to 130 deg C., formedwherein said semi-porous intermediate membrane is transverse stretchedat a temperature of 100 to 130 deg C. at a speed of 100 ft/minute, andpreferably at a speed of 50 ft/minute, wherein membrane is thermallyrelaxed at 120 to 140 deg C., and/or wherein membrane is heat treated ata temperature of 60 to 100 deg C. for preferably 8 hours to 2 to 3 days,and/or improved microporous battery separator membranes, separators,cells, or batteries including such membranes, separators, or cells,and/or methods including methods of making such membranes, separators,cells, and/or batteries, and/or methods of using such membranes,separators, cells, and/or batteries, a battery separator for a secondaryor rechargeable lithium battery which may have low electrical resistanceof less than 0.95 ohm-cm², in some cases, less than 0.8 ohm-cm², thebattery separator membrane or separator providing a means to achieve animproved level of battery performance in a rechargeable or secondarylithium battery based on a possibly synergistic combination of lowelectrical resistance, low Gurley, low tortuosity, and/or a uniqueshaped pore, which pore, in some cases, approximates the shape of atrapezoid or is trapezoid-like in shape, and/or multilayer embodiments(by way of example only, a trilayer membrane made of two polypropylenelayers with a polyethylene layer in between), wherein the microporousmembrane or battery separator having excellent onset of thermal shutdownand/or excellent rate of thermal shutdown performance as shown ordescribed herein, and/or the like.

Disclosed are novel or improved microporous battery separator membranes,separators, cells, batteries including such membranes, separators, orcells, and/or methods of making such membranes and/or separators, and/ormethods of using such membranes and/or separators. In accordance with atleast certain embodiments, an improved or novel battery separator for asecondary or rechargeable lithium battery may have low Electricalresistance of less than 0.95 ohm-cm², or in some cases, less than 0.8ohm-cm². Furthermore, the inventive battery separator membrane mayprovide a means to achieve an improved level of battery performance in arechargeable or secondary lithium battery based on a possiblysynergistic combination of low Electrical resistance, low Gurley, lowtortuosity, and/or a unique trapezoid shaped pore. In accordance with atleast certain multilayer embodiments (by way of example only, a trilayermembrane made of two polypropylene layers with a polyethylene layer inbetween), the inventive microporous membrane or battery separator mayhave excellent onset and rate of thermal shutdown performance.

The scope of the invention is not limited to the above description orexamples, or to the attached drawings. The microporous battery separatormembranes, separators, cells, batteries including such membranes,separators, or cells, and/or methods of making such membranes and/orseparators, and/or methods of using such membranes and/or separators,and/or compositions and methods of the appended claims are not limitedin scope by the specific examples, compositions and methods describedherein, which are intended as illustrations of a few aspects of theclaims and any compositions and methods that are functionally equivalentare intended to fall within the scope of the claims. Variousmodifications of the products, compositions and methods in addition tothose shown and described herein are intended to fall within the scopeof the appended claims. Further, while only certain representativeproducts, compositions and method steps disclosed herein arespecifically described, other combinations of the components,compositions and method steps also are intended to fall within the scopeof the appended claims, even if not specifically recited. Thus, acombination of steps, elements, components, or constituents may beexplicitly mentioned herein or less, however, other combinations ofsteps, elements, components, and constituents are included, even thoughnot explicitly stated. The term “comprising” and variations thereof asused herein is used synonymously with the term “including” andvariations thereof and are open, non-limiting terms. Although the terms“comprising” and “including” have been used herein to describe variousembodiments, the terms “consisting essentially of” and “consisting of”can be used in place of “comprising” and “including” to provide for morespecific embodiments of the invention and are also disclosed. Other thanin the examples, or where otherwise noted, all numbers expressingquantities of ingredients, reaction conditions, and so forth used in thespecification and claims are to be understood at the very least, and notas an attempt to limit the application of the doctrine of equivalents tothe scope of the claims, to be construed in light of the number ofsignificant digits and ordinary rounding approaches. principles,preferred embodiments and examples of operation of the present inventionhave been described in the foregoing specification. The invention whichis intended to be protected herein, however, is not to be construed aslimited to the particular forms disclosed, since these are to beregarded as illustrative rather than restrictive. Variations and changesmay be made by those skilled in the art without departing from thespirit of the present invention.

We claim:
 1. A biaxially-stretched dry-process microporous membrane,wherein the membrane was stretched in the machine direction (MD) and inthe transverse direction (TD), and stretching in the TD uses a stretchratio of 15% to 100%; wherein the biaxially-stretched dry-processmicroporous membrane has an electrical resistance less than 0.95ohm-cm².
 2. The biaxially-stretched dry-process microporous membrane ofclaim 1, wherein stretching in the TD uses a stretch ratio of 20% to100%.
 3. The biaxially-stretched dry-process microporous membrane ofclaim 2, wherein the membrane comprises non-round shaped pores.
 4. Thebiaxially-stretched dry-process microporous membrane of claim 2, whereinthe membrane comprises trapezoidal pores.
 5. The biaxially-stretcheddry-process microporous membrane of claim 1, wherein stretching in theTD uses a stretch ratio of 25% to 100%.
 6. The biaxially-stretcheddry-process microporous membrane of claim 5, wherein the membranecomprises non-round shaped pores.
 7. The biaxially-stretched dry-processmicroporous membrane of claim 5, wherein the membrane comprisestrapezoidal pores.
 8. The biaxially-stretched dry-process microporousmembrane of claim 1, wherein the membrane comprises non-round shapedpores.
 9. The biaxially-stretched dry-process microporous membrane ofclaim 1, wherein the membrane comprises trapezoidal pores.
 10. Thebiaxially-stretched dry-process microporous membrane of claim 1, havinga Gurley less than 500 sec/100 cc.
 11. The biaxially-stretcheddry-process microporous membrane of claim 1, having a tortuosity lessthan 1.5.
 12. A battery separator comprising the biaxially-stretcheddry-process microporous membrane of claim
 1. 13. A battery comprisingthe separator of claim
 12. 14. A battery cell comprising the separatorof claim
 12. 15. A battery separator for a rechargeable or secondarylithium battery comprising the biaxially-stretched dry-processmicroporous membrane of claim 1 and having Gurley of less than 150seconds/100cc, tortuosity of less than 1.2, trapezoid shaped pores, orcombinations thereof.
 16. A multilayer battery separator for arechargeable or secondary lithium battery comprising thebiaxially-stretched dry-process microporous membrane of claim
 1. 17. Thebiaxially-stretched dry-process microporous membrane of claim 1 havingan electrical resistance of less than 0.70 ohm-cm².
 18. Thebiaxially-stretched dry-process microporous membrane of claim 1 havingan electrical resistance of less than 0.60 ohm-cm².